CN102793948A - Biomedical calcium phosphate/zinc oxide nano-rod array composite coating on surface of medical metal and preparation method thereof - Google Patents
Biomedical calcium phosphate/zinc oxide nano-rod array composite coating on surface of medical metal and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a biomedical calcium phosphate/zinc oxide nano-rod array composite coating on the surface of a medical metal and a preparation method thereof. The biomedical calcium phosphate/zinc oxide nano-rod array composite coating is obtained by compounding biomedical calcium phosphate and a zinc oxide nano-rod array growing on the surface of a medical metal. One part of the biomedical calcium phosphate/zinc oxide nano-rod array composite coating comprises exposed zinc oxide nano-rod tips and the other part comprises calcium phosphate wrapping zinc oxide nano-rods. The biomedical calcium phosphate/zinc oxide nano-rod array composite coating has light-adjustable surface hydrophilicity and zinc ion slow-release properties. The preparation method comprises the following steps that a zinc oxide nano-rod array grows on the surface of a medical metal matrix with a zinc oxide crystal seed layer by a hydrothermal method; and a calcium phosphate coating is prepared by a sol-gel spin-coating method or a dip-coating method so that a part of zinc oxide nano-rods are exposed and calcium phosphate can wrap and strengthen the zinc oxide nano-rods. The biomedical calcium phosphate/zinc oxide nano-rod array composite coating has adjustable surface hydrophilicity and zinc ion slow-release properties and can be widely used for medical metal implants and other biomedical engineering fields.
Description
Technical field
The present invention relates to a kind of bio-medical coating, the bio-medical calcium phosphate/nanometic zinc oxide rod array composite coating on particularly a kind of medical metal surface.
Background technology
The bio-medical metal implant is being brought into play irreplaceable effect in the tissue repair field.Wherein, the improvement of implant surfaces characteristic is initially adhered to, breeds, is broken up for cell, and forms cell connection etc. and play crucial effects, and the variation of these cell behaviors will directly influence the performance of implant.Usually, this type coating for hydroxyapatite, OCP etc. be representative with the similar calcium phosphate coating of body bone tissue inorganic composition, like Chinese patent CN 201110134974.5 coatings prepared.Discovering in recent years; If the hydrophilic enhancing of coating surface can make implant interface ossification that significant enhancing (T. Ueno is arranged; Et al. Enhancement of bone – titanium integration profile with UV-photo functionalized titanium in a gap healing model, Biomaterials 31 (2010) 1546-1557); Utilize this this type coating of material preparation to become an important directions of this type coating development in recent years with biocompatibility and ultra water-wet behavior.Prepared nano-TiO with good biocompatibility like Chinese patent CN 201010253123.8
2Coating or the like.In addition; Discover that in a large number an amount of metal ion is like zinc ion; Suitable concentration can promote near the regeneration of the osseous tissue of embedded material effectively; And has an antiinflammatory action (X. Li, et al. The optimum zinc content in set calcium phosphate cement for promoting bone formation in vivo, Materials Science and Engineering C 29 (2009) 969 – 975).Chinese patent CN 200510061526.1 utilizes these characteristics to have zinc ion sustained release performance calcium phosphate powder.
In sum, if a kind of composite coating based on calcium phosphate can have this several kinds of performances concurrently, can improve the performance of bio-medical metal implant and tissue bond more effectively.Although zinc ion can be introduced in the calcium phosphate coating, the water-wet behavior of calcium phosphate coating itself is not good, and the adjusting of its surperficial hydrophobic water-wet behavior is also comparatively difficult.Therefore, the coating that has above-mentioned characteristic concurrently also is difficult to realize at present.
Summary of the invention
The objective of the invention is in order to overcome the deficiency of prior art, the bio-medical calcium phosphate/nanometic zinc oxide rod array composite coating on a kind of medical metal surface and preparation method thereof is provided.
Bio-medical calcium phosphate/nanometic zinc oxide rod array the composite coating on medical metal surface; Be to be composited by bio-medical calcium phosphate and the nanometic zinc oxide rod array that is grown in the medical metal surface; The part of composite coating is most advanced and sophisticated for the zinc oxide nano rod that exposes, and all the other are partly for wrapping up the calcium phosphate of zinc oxide nano rod; Described composite coating has photic adjustable surface hydrophilic characteristic and zinc ion slow release characteristic concurrently.
Described medical metal is medical metallic titanium or its alloy, medical stainless steel or medical cochrome.
Described bio-medical calcium phosphate is hydroxyapatite or beta-tricalcium phosphate or OCP or calcium hydrogen phosphate or fluoridated hydroxyapatite.
The described diameter that grows in nanometer rods in the oxidation on metal surface zinc nanometer stick array is 20 ~ 80 nm, highly is 300 ~ 1500 nm.
The thickness of described composite coating is 200 ~ 1400 nm.
The method for preparing of described coating comprises following step:
1) preparation is grown in oxidation on metal surface zinc nanometer stick array:
A. with zinc acetate and ethanolamine in molar ratio 1:1 be dissolved in the ethanol; Compound concentration is the zinc acetate of 0.05M ~ 0.1M and the alcoholic solution of ethanolamine; Get the alcoholic solution of 10 μ L ~ 20 these zinc acetates of μ L and ethanolamine and be spun on the medical metal surface with 5000rpm ~ 7000rpm; Spin coating finishes to be placed on 400 ℃ ~ 600 ℃ following heat treatment 0.5h ~ 1.5h, and it is subsequent use to form the medical metal surface that possesses the zinc oxide crystal seed layer;
B. 1:1 is soluble in water in molar ratio with zinc nitrate and hexamethylenetetramine; Configuration concentration is the growth mother liquid of hydro-thermal reaction of zinc nitrate and the hexamethylenetetramine of 0.02M ~ 0.1M; Agitated reactor is put into growth mother liquid in the medical metal surface that will possess the zinc oxide crystal seed layer; Behind insulation 2h ~ 6h under 80 ℃ ~ 120 ℃, the use deionized water cleans the medical metal surface and carries out dried, obtains being grown in oxidation on metal surface zinc nanometer stick array;
2) the bio-medical calcium phosphate/nanometic zinc oxide rod array composite coating on preparation medical metal surface:
Lime nitrate and phosphorus pentoxide are dissolved in ethanol, and to be mixed with calcium concentration be 0.1M ~ 1M; Calcium phosphorus mol ratio is 1.5 ~ 1.67 precursor solution; Get 10 μ L ~ this precursor solution of 20 μ L and be grown in oxidation on metal surface zinc nanometer stick array surface with what 1000rpm ~ 3000rpm was spun on that step 1) obtains; Spin coating finishes to be placed on 500 ℃ ~ 700 ℃ following heat treatment 10min ~ 50 min; Be dipped in then in hydrochloric acid that concentration is 0.001M ~ 0.1M or the citric acid solution and take out after 1 ~ 60 second, and more than three times, obtain the bio-medical calcium phosphate/nanometic zinc oxide rod array composite coating on medical metal surface with deionized water rinsing rapidly.
Beneficial effect of the present invention: calcium phosphate, ultra water-wet behavior and functional ion slow release are combined dexterously; At first, form the most advanced and sophisticated composite coating that exposes of zinc oxide nano rod through preparation calcium phosphate in the nanometic zinc oxide rod array gap then at medical metal superficial growth nanometic zinc oxide rod array.The coating of preparing had both had the good biological nature of calcium phosphate, had zinc oxide can present water-wet behavior under irradiation under ultraviolet ray characteristics again, and can be through the water-wet behavior of the isoparametric adjustment regulation and control of time of ultraviolet irradiation composite coating.And along with contacting of coating and body fluid, zinc oxide can slowly discharge through dissolving, and performance promotes the effect of skeletonization.What is more important, the parcel of calcium phosphate make the zinc oxide strong bonded in matrix surface, guarantee that it can't come off with nanometer rods or form of nanoparticles to get into human body and have a negative impact.
Description of drawings
Fig. 1 is the surface topography (a) and cross-section morphology (b) figure of the bio-medical calcium phosphate/nanometic zinc oxide rod array composite coating on medical metal surface;
Fig. 2 is the ultra-vioket radiation front and rear surfaces water contact angle figure of the bio-medical calcium phosphate/nanometic zinc oxide rod array composite coating on medical metal surface;
Fig. 3 is the Zn ion releasing curve diagram of bio-medical calcium phosphate/nanometic zinc oxide rod array composite coating in the TRIS buffer on medical metal surface;
Fig. 4 is the SEM figure of the bio-medical calcium phosphate/nanometic zinc oxide rod array composite coating on medical metal surface.
The specific embodiment
Further specify the present invention below in conjunction with accompanying drawing and embodiment.
Bio-medical calcium phosphate/nanometic zinc oxide rod array the composite coating on medical metal surface; Be to be composited by bio-medical calcium phosphate and the nanometic zinc oxide rod array that is grown in the medical metal surface; The part of composite coating is most advanced and sophisticated for the zinc oxide nano rod that exposes, and all the other are partly for wrapping up the calcium phosphate of zinc oxide nano rod; Described composite coating has photic adjustable surface hydrophilic characteristic and zinc ion slow release characteristic concurrently.
Described medical metal is medical metallic titanium or its alloy, medical stainless steel or medical cochrome.
Described bio-medical calcium phosphate is hydroxyapatite or beta-tricalcium phosphate or OCP or calcium hydrogen phosphate or fluoridated hydroxyapatite.
The described diameter that grows in nanometer rods in the oxidation on metal surface zinc nanometer stick array is 20 ~ 80 nm, highly is 300 ~ 1500 nm.
The thickness of described composite coating is 200 ~ 1400 nm.
Embodiment 1
1) preparation is grown in oxidation on metal surface zinc nanometer stick array:
A. with zinc acetate and ethanolamine in molar ratio 1:1 be dissolved in the ethanol; Compound concentration is the zinc acetate of 0.1M and the alcoholic solution of ethanolamine; Get the alcoholic solution of 10 these zinc acetates of μ L and ethanolamine and be spun on the medical metal surface with 5000rpm; Spin coating finishes to be placed on 400 ℃ of following heat treatment 0.5h, and it is subsequent use to form the medical metal surface that possesses the zinc oxide crystal seed layer;
B. 1:1 is soluble in water in molar ratio with zinc nitrate and hexamethylenetetramine; Configuration concentration is the growth mother liquid of hydro-thermal reaction of zinc nitrate and the hexamethylenetetramine of 0.02M; Agitated reactor is put into growth mother liquid in the medical metal surface that will possess the zinc oxide crystal seed layer; Behind insulation 2h under 80 ℃, the use deionized water cleans the medical metal surface and carries out dried, obtains being grown in oxidation on metal surface zinc nanometer stick array;
2) the bio-medical calcium phosphate/nanometic zinc oxide rod array composite coating on preparation medical metal surface:
Lime nitrate and phosphorus pentoxide are dissolved in ethanol, and to be mixed with calcium concentration be 0.5M; Calcium-phosphorus ratio is 1.67 precursor solution; Get this precursor solution of 10 μ L and be spun on the sample surfaces that step 1) obtains with 3000rpm, spin coating finishes to be placed on 500 ℃ of following heat treatment 10min.Be dipped in then in the hydrochloric acid solution that concentration is 0.001M and take out after 1 second, and more than three times, obtain the bio-medical calcium phosphate/nanometic zinc oxide rod array composite coating on medical metal surface with deionized water rinsing rapidly.
Nanometic zinc oxide rod array is wrapped up by hydroxyapatite in the bio-medical calcium phosphate/nanometic zinc oxide rod array composite coating on medical metal surface; The part of nanometer rods is exposed to coating outer (Fig. 1); After the dark processing 3 days, the surface water contact angle be 108 ° (Fig. 2 a), through behind the ultra-vioket radiation 30min; Its surface water contact angle becomes 37 ° (Fig. 2 b), demonstrates the response characteristic to ultraviolet light.
In order to test the biological stability of this coating; Use simulation biological fluid TRIS buffer sample to be carried out the immersion of different durations; The Zn ion release profiles that obtains is as shown in Figure 3; The release ratio of Zn ion in the TRIS buffer is milder, a large amount of release of initial stage do not occur, and burst size is well below the Zn ion concentration that makes the biological cell intoxicating (6.0 μ g/ml).
Embodiment 2
1) preparation is grown in oxidation on metal surface zinc nanometer stick array:
A. with zinc acetate and ethanolamine in molar ratio 1:1 be dissolved in the ethanol; Compound concentration is the zinc acetate of 0.75M and the alcoholic solution of ethanolamine; Get this precursor solution of 10 μ L and be spun on metallic substrate surfaces with 5000rpm; Spin coating finishes to be placed on 400 ℃ of following heat treatment 0.5h, forms the zinc oxide crystal seed layer;
B. 1:1 is soluble in water in molar ratio with zinc nitrate and hexamethylenetetramine; Configuration concentration is the growth mother liquid of hydro-thermal reaction of zinc nitrate and the hexamethylenetetramine of 0.02M; Sample for preparing among a and growth mother liquid are put into agitated reactor; Be incubated 6h down at 80 ℃, the taking-up substrate uses deionized water that sample surfaces is cleaned and carries out dried, promptly obtains being grown in oxidation on metal surface zinc nanometer stick array;
2) the bio-medical calcium phosphate/nanometic zinc oxide rod array composite coating on preparation medical metal surface:
Lime nitrate and phosphorus pentoxide are dissolved in ethanol, and to be mixed with calcium concentration be 0.1M; Calcium-phosphorus ratio is 1.67 precursor solution; Get this precursor solution of 15 μ L and be spun on the sample surfaces that step 1) obtains with 3000rpm, spin coating finishes to be placed on 500 ℃ of following heat treatment 15min.Be dipped in then in the citric acid solution that concentration is 0.001M and take out after 1 second; And more than three times, promptly obtain the said photic adjustable water-wet behavior and the bio-medical calcium phosphate/nanometic zinc oxide rod array composite coating of zinc ion slow release characteristic of having concurrently with deionized water rinsing rapidly.
Nanometic zinc oxide rod array is wrapped up by hydroxyapatite in the composite micro-nano rice structure coating, and the part of nanometer rods is exposed to coating outer (Fig. 4)
Embodiment 3
1) preparation is grown in oxidation on metal surface zinc nanometer stick array:
A. with zinc acetate and ethanolamine in molar ratio 1:1 be dissolved in the ethanol; Compound concentration is the zinc acetate of 0.05M and the alcoholic solution of ethanolamine; Get this precursor solution of 20 μ L and be spun on metallic substrate surfaces with 7000rpm; Spin coating finishes to be placed on 400 ℃ of following heat treatment 1h, forms the zinc oxide crystal seed layer;
B. 1:1 is soluble in water in molar ratio with zinc nitrate and hexamethylenetetramine; Configuration concentration is the growth mother liquid of hydro-thermal reaction of zinc nitrate and the hexamethylenetetramine of 0.05M; Sample for preparing among a and growth mother liquid are put into agitated reactor; Be incubated 2h down at 100 ℃, the taking-up substrate uses deionized water that sample surfaces is cleaned and carries out dried, promptly obtains being grown in oxidation on metal surface zinc nanometer stick array;
2) the bio-medical calcium phosphate/nanometic zinc oxide rod array composite coating on preparation medical metal surface
Lime nitrate and phosphorus pentoxide are dissolved in ethanol, and to be mixed with calcium concentration be 0.5M; Calcium-phosphorus ratio is 1.67 precursor solution; Get this precursor solution of 10 μ L and be spun on the sample surfaces that step 1) obtains with 1000rpm, spin coating finishes to be placed on 700 ℃ of following heat treatment 10min.Be dipped in then in the citric acid solution that concentration is 0.1M and take out after 1 second, and more than three times, promptly obtain the bio-medical calcium phosphate/nanometic zinc oxide rod array composite coating on medical metal surface with deionized water rinsing rapidly.
Embodiment 4
1) preparation is grown in oxidation on metal surface zinc nanometer stick array:
A. with zinc acetate and ethanolamine in molar ratio 1:1 be dissolved in the ethanol; Compound concentration is the zinc acetate of 0.1M and the alcoholic solution of ethanolamine; Get this precursor solution of 15 μ L and be spun on metallic substrate surfaces with 7000rpm; Spin coating finishes to be placed on 700 ℃ of following heat treatment 1.5h, forms the zinc oxide crystal seed layer;
B. 1:1 is soluble in water in molar ratio with zinc nitrate and hexamethylenetetramine; Configuration concentration is the growth mother liquid of hydro-thermal reaction of zinc nitrate and the hexamethylenetetramine of 0.1M; Sample for preparing among a and growth mother liquid are put into agitated reactor; Be incubated 2h down at 80 ℃, the taking-up substrate uses deionized water that sample surfaces is cleaned and carries out dried, promptly obtains being grown in oxidation on metal surface zinc nanometer stick array;
2) the bio-medical calcium phosphate/nanometic zinc oxide rod array composite coating on preparation medical metal surface
Lime nitrate and phosphorus pentoxide are dissolved in ethanol, and to be mixed with calcium concentration be 1M; Calcium-phosphorus ratio is 1.67 precursor solution; Get this precursor solution of 20 μ L and be spun on the sample surfaces that step 1) obtains with 2000rpm, spin coating finishes to be placed on 500 ℃ of following heat treatment 50min.Be dipped in then in the hydrochloric acid solution that concentration is 0.01M and take out after 30 seconds, and more than three times, promptly obtain the bio-medical calcium phosphate/nanometic zinc oxide rod array composite coating on medical metal surface with deionized water rinsing rapidly.
Embodiment 5
1) preparation is grown in oxidation on metal surface zinc nanometer stick array:
A. with zinc acetate and ethanolamine in molar ratio 1:1 be dissolved in the ethanol; Compound concentration is the zinc acetate of 0.1M and the alcoholic solution of ethanolamine; Get this precursor solution of 10 μ L and be spun on metallic substrate surfaces with 6000rpm; Spin coating finishes to be placed on 500 ℃ of following heat treatment 0.5h, forms the zinc oxide crystal seed layer;
B. 1:1 is soluble in water in molar ratio with zinc nitrate and hexamethylenetetramine; Configuration concentration is the growth mother liquid of hydro-thermal reaction of zinc nitrate and the hexamethylenetetramine of 0.02M; Sample for preparing among a and growth mother liquid are put into agitated reactor; Be incubated 4h down at 120 ℃, the taking-up substrate uses deionized water that sample surfaces is cleaned and carries out dried, promptly obtains being grown in oxidation on metal surface zinc nanometer stick array;
2) the bio-medical calcium phosphate/nanometic zinc oxide rod array composite coating on preparation medical metal surface
Lime nitrate and phosphorus pentoxide are dissolved in ethanol, and to be mixed with calcium concentration be 0.5M; Calcium-phosphorus ratio is 1.5 precursor solution; Get this precursor solution of 20 μ L and be spun on the sample surfaces that step 1) obtains with 3000rpm, spin coating finishes to be placed on 500 ℃ of following heat treatment 30min.Be dipped in then in the hydrochloric acid solution that concentration is 0.001M and take out after 60 seconds, and more than three times, promptly obtain the bio-medical calcium phosphate/nanometic zinc oxide rod array composite coating on medical metal surface with deionized water rinsing rapidly.
Embodiment 6
1) preparation is grown in oxidation on metal surface zinc nanometer stick array:
A. with zinc acetate and ethanolamine in molar ratio 1:1 be dissolved in the ethanol; Compound concentration is the zinc acetate of 0.05M and the alcoholic solution of ethanolamine; Get this precursor solution of 10 μ L and be spun on metallic substrate surfaces with 7000rpm; Spin coating finishes to be placed on 600 ℃ of following heat treatment 1h, forms the zinc oxide crystal seed layer;
B. 1:1 is soluble in water in molar ratio with zinc nitrate and hexamethylenetetramine; Configuration concentration is the growth mother liquid of hydro-thermal reaction of zinc nitrate and the hexamethylenetetramine of 0.02M; Sample for preparing among a and growth mother liquid are put into agitated reactor; Be incubated 2h down at 80 ℃, the taking-up substrate uses deionized water that sample surfaces is cleaned and carries out dried, promptly obtains being grown in oxidation on metal surface zinc nanometer stick array;
2) the bio-medical calcium phosphate/nanometic zinc oxide rod array composite coating on preparation medical metal surface
Lime nitrate and phosphorus pentoxide are dissolved in ethanol, and to be mixed with calcium concentration be 0.3M; Calcium-phosphorus ratio is 1.67 precursor solution; Get this precursor solution of 10 μ L and be spun on the sample surfaces that step 1) obtains with 1000rpm, spin coating finishes to be placed on 600 ℃ of following heat treatment 10min.Be dipped in then in the citric acid solution that concentration is 0.001M and take out after 60 seconds, and more than three times, promptly obtain the bio-medical calcium phosphate/nanometic zinc oxide rod array composite coating on medical metal surface with deionized water rinsing rapidly.
The present invention combines calcium phosphate, ultra water-wet behavior and functional ion slow release dexterously; At first, form the most advanced and sophisticated composite coating that exposes of zinc oxide nano rod through preparation calcium phosphate in the nanometic zinc oxide rod array gap then at medical metal superficial growth nanometic zinc oxide rod array.The coating of preparing is in the good biological nature that keeps calcium phosphate; The coating surface water-wet behavior can be through the ultraviolet light response property regulation and control of zinc peroxide nanometer rods; And zinc ion can realize having concurrently the coating of these several specific characters preferably through zinc oxide dissolving slow release.The present invention is not limited to above embodiment, and some all should be thought within protection scope of the present invention based on technical scheme modification of the present invention.
Claims (6)
1. the bio-medical calcium phosphate/nanometic zinc oxide rod array composite coating on medical metal surface; It is characterized in that: composite coating is to be composited by bio-medical calcium phosphate and the nanometic zinc oxide rod array that is grown in the medical metal surface; The part of composite coating is most advanced and sophisticated for the zinc oxide nano rod that exposes, and all the other are partly for wrapping up the calcium phosphate of zinc oxide nano rod; Described composite coating has photic adjustable surface hydrophilic characteristic and zinc ion slow release characteristic concurrently.
2. coating according to claim 1 is characterized in that: described medical metal is medical metallic titanium or its alloy, medical stainless steel or medical cochrome.
3. coating according to claim 1 is characterized in that: described bio-medical calcium phosphate is hydroxyapatite or beta-tricalcium phosphate or OCP or calcium hydrogen phosphate or fluoridated hydroxyapatite.
4. coating according to claim 1 is characterized in that: the described diameter that grows in nanometer rods in the oxidation on metal surface zinc nanometer stick array is 20 ~ 80 nm, highly is 300 ~ 1500 nm.
5. coating according to claim 1 is characterized in that: the thickness of described composite coating is 200 ~ 1400 nm.
6. the method for preparing of a coating according to claim 1 is characterized in that: comprise following step:
Preparation is grown in oxidation on metal surface zinc nanometer stick array:
A. with zinc acetate and ethanolamine in molar ratio 1:1 be dissolved in the ethanol; Compound concentration is the zinc acetate of 0.05M ~ 0.1M and the alcoholic solution of ethanolamine; Get the alcoholic solution of 10 μ L ~ 20 these zinc acetates of μ L and ethanolamine and be spun on the medical metal surface with 5000rpm ~ 7000rpm; Spin coating finishes to be placed on 400 ℃ ~ 600 ℃ following heat treatment 0.5h ~ 1.5h, and it is subsequent use to form the medical metal surface that possesses the zinc oxide crystal seed layer;
B. 1:1 is soluble in water in molar ratio with zinc nitrate and hexamethylenetetramine; Configuration concentration is the growth mother liquid of hydro-thermal reaction of zinc nitrate and the hexamethylenetetramine of 0.02M ~ 0.1M; Agitated reactor is put into growth mother liquid in the medical metal surface that will possess the zinc oxide crystal seed layer; Behind insulation 2h ~ 6h under 80 ℃ ~ 120 ℃, the use deionized water cleans the medical metal surface and carries out dried, obtains being grown in oxidation on metal surface zinc nanometer stick array;
Bio-medical calcium phosphate/nanometic zinc oxide rod array the composite coating on preparation medical metal surface:
Lime nitrate and phosphorus pentoxide are dissolved in ethanol, and to be mixed with calcium concentration be 0.1M ~ 1M; Calcium phosphorus mol ratio is 1.5 ~ 1.67 precursor solution; Get 10 μ L ~ this precursor solution of 20 μ L and be grown in oxidation on metal surface zinc nanometer stick array surface with what 1000rpm ~ 3000rpm was spun on that step 1) obtains; Spin coating finishes to be placed on 500 ℃ ~ 700 ℃ following heat treatment 10min ~ 50 min; Be dipped in then in hydrochloric acid that concentration is 0.001M ~ 0.1M or the citric acid solution and take out after 1 ~ 60 second, and more than three times, obtain the bio-medical calcium phosphate/nanometic zinc oxide rod array composite coating on medical metal surface with deionized water rinsing rapidly.
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